Contacting solid particles with gaseous fluids



April 15, 1952 H. J.

oGoRzALY 2,593,338

CONTACTING SOLID PARTICLES WITH GASEOUS FLUIDS REACTOR STRIPPING GAS /FLUIDIZING GAS Patented Apr. 15, 1952 CONTACTING SOLID PARTICLES WITH GASEOUS FLUIDS Henry J. Ogorzaly, Summit, N` J., assigner to Standard Oil Development Company, a corporation of Delaware Application January 28, 1947, Serial No. 724,760

3 Claims.

This invention relates to catalytic operations using powdered catalyst or contact material, wherein the particles are circulated by means of hydrostatic pressure developed in standpipes, and more particularly relates to reducing erosion Aof slide valves in the standpipes, which valves are used to control the flow of the powdered material from the standpipes.

My invention may be used in processes usingl powdered contact material and in catalytic operations generally, where powdered catalyst is circulated by means of hydrostatic pressure developed in standpipes having slide control valves, but it will be specifically described in connection with the catalytic conversion of hydrocarbons.

The rate oi ow oi iiuidized catalysts or other solids from a standpipe is ordinarily controlled by the use of a slide valve to control the area for passage of the solids from the standpipe. These valves are subject to severely erosive conditions, and their failure may be the cause for bringing a unit off-stream. A large part of the erosion results from excessive pressure-drop across the slide valves, and this high pressure differential in turn results from the fact that standpipes of adequate length to insure circulation with fresh catalyst or contact particles may generate excessive pressures duringthe course of the operation of the unit,

In constructing fluid catalyst units using powdered catalyst, the units are designed for fresh catalyst, of a given type, for certain pressures and bed levels in the reaction and regeneration vessels, for certain pressure-drops across the slide valves controlling the flow of solids from the standpipes and for certain pressuredrops in catalyst and recycle lines. The standpipes are designed and constructed of suicient height to develop the hydrostatic pressure at the base of the standppe which will be sufficient to overcome pressure-drops through the system.

Numerous changes may occur during operation which result in higher pressures being developed by the standpipe and consequently greater pressure-drops across the slide valves,- which cause increased erosion of the control slide valves. For example, after extended use. in the unit, the

catalyst becomes more dense, and this results in V higher standpipe pressures. In addition, fresh catalyst contains fines, and fiuidized fresh catalyst will have a lower density than fluidized catalystwhich has been used for some time in the unit, becaust of the lcss of nes from the system;

and as a result, the used catalyst forms a more dense iiuidized mixture and builds up higher pressures at the base of the standpipes.

In bottom draw-off units where dense fluidized catalyst is withdrawn from the bottom portion of the dense iiuidized mixture or bed in a contacting zone, the height of the mixture or bed in the contacting zone builds up a hydrostatic pressure which is added to the hydrostatic pressure developed by the column cf fluidized solids in the standppes. The unit may be designed for one duid bed thickness and may later be operated with a deeper fluidized bed of greater thickness in the contacting zone. This will also result in a greater pressure being developed by the standpipe and a greater pressure-drop across the slide valve, and consequently, there will be more erosion of the slide valve.

Frequently, operating conditions require Shifting the pressure in one contacting vessel or another to a different level than anticipated in the design. A change of this type is directly reflected in the pressure drop across the Slide valve controlling the ow cf catalyst to or from this vessel.

Similarly, operating conditions may dictate the circulation of greater or lesser amounts of catalyst, or the utilization of variable quantities of carrier gas in the catalyst transfer lines, The resulting variation in pressure drop in these transfer lines is also reflected in the differential pressure across the slide valves.

In some cases, the uidized catalyst unit may be designed and constructed for one type of catalyst, and the unit later operated on a denser catalyst which will give higher pressures at the base of the standpipes and more erosion of the slide valves.

According to my invention, the pressure differential across a slide valve is reduced during the run 01 operation of the unit by having previously installed a constriction such as an prince, or preferably a Venturi-type throat with gradually constricting inlet and expanding egress, etc. in the, line below a slide valve discharging from a standpipe into a stream of carrier vapors cr gases. The pressure below the slide valve and above the constriction will be gre Vter than ifl the constriction were not installed, and therefore the lipressure differential across the Slide valve is reduced.

According to an improved forni my invern tion, the constriction is installed in the l' low the slide valve as mentioned paragraph, butin addition, connections or lines are installed to permit proportioning of the now of carrier gas or vapor between two points of injection, one between the constriction and the slide valve and one after the constriction. By changing the amount of gas or vapor introduced into the line above the constriction, the pressure differential across the constriction may be varied and the pressure differential across the slide valve may be controlled at Vany desired value, as may be required to minimize erosion, independently of shifts in the operating conditions of the unit.

If the pressure differential across the slide valve is increased for any reason, more gas or vapor is introduced above the constriction and below the slide valve, and by forcing more gas or vapor through the constriction, there will be a greater pressure differential across the constriction and a lessened pressure drop across the slide valve. If the differential pressure across the slide valve decreases to below the differential desired for safety or necessary to pass the required amount of catalyst, the amount of gas or vapor being passed into the pipe above the constriction and below the slide valve will be decreased.

The rest of the gas or vapor is mixed with the catalyst or contact material after it has passed through the constriction and the resulting mixture crvsuspension is passed to the proper contacting zone for further treatment.

In the drawing, the figure represents one form of apparatus which may be used in carrying out my invention. Y

- Referring now to the drawing', the reference character l designates a cylindrical reaction or contacting zone having a conical bottom II and an inlet l2 for introducing gaseous iuid and solid particles into the vessel I0. In the specic form of the apparatus shown in the drawing, hot, regenerated catalyst or contact particles are introduced into line i2 from line I4. The feed is introduced into line i2 from main line I6 having branch lines i8 and 20. The-branch line I8 has a valve 22 for controlling the amount of feed introduced into line I2. The other branch line selected to maintain the catalyst particles in a dense, uidized, liquid-simulating, turbulent condition shown at 32, and having a level indicated at 34 with a dilute or less dense suspension thereabove indicated at 36. The superficial velocity of the gaseous fluid or hydrocarbon vapors passing upwardly through the vessel H3 is the velocity of the gas or vapor in a vessel free of solids, and is preferably between about 0.2 foot per second and 2.0 feet per second, preferably 0.5-1.5 feet per second.

In the catalytic cracking of hydrocarbons, the cracking catalyst may comprise acid-treated bentonite clays, synthetic silica-alumina gels, synthetic silica-magnesia gels, and the like. The synthetically prepared catalyst may also be in .the form of small spheres.

20 has a valve 2s for controlling the flow of feed plate or grid member 28, for distributing the gaseous fluid and solid particles evenly across the reaction or contacting vessel l0. Instead of introducing Vthe gaseous iiuid and solidV particles through a common inlet, the gaseous fluid and solid particles may be separately introduced into the vessel l0. v

The inverted conical feed member ZY is arranged in the lower part of the reaction vessel l0, and is spaced from the inner wall of the vessel toA provide an annular space 30 for withdrawing solid particles as a dense uidized mix- .ture from the lower portion of the Vessel l0.

In a catalytic cnversion operation, the oil feed introduced through lines I6 and i8 maycomprise vaporous or'liquid hydrocarbons such as gas oil, heavy or light naphtha, etc., or may comprise preheated reduced Vcrude petroleum oil. Where the hydrocarbon feed is only partially preheated, the heat of vaporization and4 cracking is supplied by usingasuflicient amount of hot, regenerated catalyst or contact particles.

The velocity of the hydrocarbon vapors passing upwardly through the reaction vessel` yI0 is In the catalytic conversion of hydrocarbons, the temperature should be between about 800 F. and 1050 F. For example, for the catalytic cracking of hydrocarbons to produce gasoline, the temperature may be between about 900 and 1000 F. The time of residence of the hydrocarbon vapors in the conversion zone may be between about 5 seconds and 50 seconds. When using the silicaalumina gels in finely-divided form, the Adensity of the nuidized mixture 32 in the vessel I0 is about 15 pounds per cubic foot to 40 pounds per cubic foot, depending upon the velocity of the upwardly flowing hydrocarbon vapors as well as theA density and particle size of the catalyst.

The vapors passing upwardly through the reaction vessel I0 entrain some solid particles as they'pass upwardly into the upper lessV dense suspension indicated at 35, and in order to ,remove most of the entrained particles, the vapors are passed through inlet 33 into separating means 40. The separating means 40 is shown as a cyclone separator arranged in the upper part of the reaction vessel I0, but other forms of separating means may be used, such as Multiclones, and if desired, the separating means may be arranged outside of the vessel l0. Also, one or more cyclone separators or other separating means may be used and' the separators may be arranged in parallel or in series. V

- In the separating means 40, most of the entrained solid particles are removed from the vaporous reaction products, the separatedparticles being returned to the dense mixture 32 by dip leg or pipe 42. The vaporous reaction products pass overhead through line 44 and are preferably passed to separation equipment for recovering desired products. In the catalytic cracking of hydrocarbons, the vaporous reaction products are preferably passed to a fractioning tower (not shown) for separating desired products such as a gasoline from higher-boiling hydrocarbons.

' The vaporous reaction products leaving the separator 40 still contain small amounts of catalyst particles which are recovered as a slurry in the condensate oil in the bottom of the fractionating tower. This catalyst comprises catalyst fines and is preferably recovered from the condensate oil by filtering, settling, etc., and the catalyst returned to the reactor or regenerator.

During the catalyst conversion of hydrocar- Y the catalyst particles, it is preferred to strip out hydrocarbons entrained with or adsorbed on the fouled or contaminated catalyst particles.

The conical bottom ll of the-vessel I Il forms a withdrawal passageway 46 with the bottom portion of the conical feed member 26, for withdrawing fouled or spent catalyst particles from the dense mixture 32. Stripping gas such as steam or` other inert gas is introduced' through one or more lines 48 into the lower portion of the annular stripping section or zone 30 for passageupwardly between the downwardly moving particles tostrip out fouled or entrainedl hydrocarbons. Fluidizing gas is introduced through line lor lines 52 into the conical bottom Ilof the vessel lll to maintain the catalystparticles'in afluidized' con*- dition as they are withdrawn' from the bottom portion of the reaction vessel Ill.

The dense iiuidized` stripped particles areintroduced into the upper portion of a standpipe 54 provided with one or more fiuidizing lines 56 for introducing fluidizing gas into the standpipe 54 for maintaining the particles in a dense iluid'- ized liquid-simulating condition, sol that the fiuidized mixture produces hydrostatic pressure at the base of the standpipe. The standpipe 54 is provided with a slide control valvev58 torreontrolling the rate of withdrawal'of catalyst part-icles from the vessel i0-, and for maintainingthe level 34 of the dense iiuidized mixture at` the desired distance from the top of the vessel Il).r In commercial units, this distance ofthe level of the fluidized mixture to the 'top of the reaction vessel is preferably maintained between about 10 feet and 20 feet to reduce by settling outV the amount of catalyst particles entrained with the A gaseous fluid leaving the top of the reaction vessel.

As the iiuidizedV particles pass through the slide valve 58, there is a certain pressure-drop so that the pressure below the slide valve'is less than the pressure above the slide valve. Incommercial units, this pressure-drop is desiredttobe about 5 pounds per square inch, i. e., theappa# ratus is designed and constructed'so that .in normal operation there will be a pressure-drop of .about 5 pounds per square inch. However, after the unit remains in operation for a relatively long period of time, the catalyst particles become more dense, catalyst fines are lost from the system, and as the catalyst drops toward an equilibrium activity level, the bed level 3'4 in reaction vessel IEI may beraised to maintain conversion, thus producing a higher pressure in the standpipe 54.

Under these conditions, the pressuredeveloped by the standpipe is greater than the design figure and the pressure-drop across the slide valve 58 will be in excess of 5 pounds. This increase in pressure-drop results in increased erosion of the slide valve, and it is the purpose of myiinvention sired to increasethe capacity of the, unit byplac-` ling the. reaction'zone under increased, pressure or superatmosphericpressure; Theadvantageof higher pressure on the reaction zone is that hydrocarbon feed may be charged to the unit at increased mass rates of iiow without exceeding velocity limitations in the reaction zone or in the fractionator directly connected to the reaction cone. Excessive velocity at these points results in increasedentrainment of powdered catalyst from the reactor of liquefied cracked products within the fractionator.

In order to maintain the pressuradrop or diflerential across the slide valve 58, I provide a constriction shown generally at 62 in the line 64 which leads from the bottom of the slide valve Eil `and which communicates with the standpipe 54. As shown in the drawing, the constriction 52 is a Venturi-type throat having a relatively long conical portion 6G and a shorter more abrupt conical portion t3 leading to the line 64 below the constriction 62. Instead of' using a venturi., an orifice may be used to produce a pressure-drop or pressure diiiersniial across a por tion of the line ed.

To provide flexibility in the pressure-drop taken across the constriction 62, it is preferred to introduce a controllable gaseous stream between slide valve 53 and constriction 82.

This may be done by subdividing the regenerating' gas such as air or other oxygen-containing gas into two streams, and feeding one stream above the constriction 62 and the other stream below the constriction 32. The regenerating gas is introduced through line l2 and a portion is passed through line la, having a valve l5, into the line E55 below the constriction 52, and the other part of ne regenerating gas is passed through line 18, having a valve 32 for introducing the regenerating gas above the constriction 62; The two streams are so proportioned as to vary the pressuredrop or pressure dilerential across the constriction E2 to compensate for changes in the pressure differential across the slide valve 58. For example, if the pressure differential across the slide valve 53 is greatly in excess of the desired ligure, more of the regenerating gas will be passed through the vaived line 'i8 above the constriction t2 to create or produce a greater pressuredrop or pressure differential across constriction thereby increasing the pressure in the line 5S above the constriction 62, so that the pressure-drop or pressure diiierential across the slide valve 58 is maintained at 5 pounds per square inch, ci' the desired design figure. The rest of the regenerating gas is passed through line ie into the bottom portion of line E4.

The contaminated par cies with the regeneratinggas are then passed upwardly through line 8d into the conical bottom portion S5 of regenerator 83 below the horiaontally arranged distribution plate or grid member 9i! therein. The regeneration vessel S8 is shown as arranged above 'ie reactor or reaction vessel Iii, but other a1'- rangements 'may be used, The grid member Si) functions to evenly distribute the catalyst particles` and the regenerating gas across the area of theregeneration vessel 88.

The superficial velocity of the regenerating gas is selected to maintain the catalyst or contact particles as a dense, luidized, liquidsimulating turbulent mixture or layer shown at 92, having a level indicated at di. Above the level 94l isa less dense or dilute suspension 96. The superficial velocity of the upfiowing regenerating gas in the vessel 55 may be between about 0.2 ioot'per second and 2.0 feet per second, and pref- Ieraizilfwabout0.5' foot per second to- 1.5 feetper i 7 Second. Using the catalyst above-described, the density of the mixture in the regeneration vessel 88 will be between about 15 -pounds per cubic foot and 40 pounds per cubic oot.

The regeneration gases passing upwardly into they dilute or less dense phase S contain entrained catalyst particles and in order to separate most of these particles, the regeneration gases are Vpassed through separating means 9 0 having an inlet 02. The separating means 98 is shown in the drawing as a cyclone separator arranged in the upper portion of the regeneration vessel 83, but if desired, the separating means may be arranged outside of the vessel 88. Other separating means may be used and more than one separating means may be used in parallel orrin series. The separated particles accumulate in the separating means 98 and are returned to-the dense bed or mixture 92 in the vessel 88 by means of a dip leg or dip pipe |06.

The regenerationgases leave the separating means 98 and pass overhead through line |05, and as they will contain some fine catalyst particles, they are preferably introduced into another separating means, such as a Cottrell precipitator (not shown). The separated particles from the precipitator may be returned to the dense-bed or mixture 92 in the vessel 08, but are preferably introduced into the standpipe extending from the bottom portion ofthe regeneration vessel 88. The temperature during regeneration may be between about 1000 F. and 1150 F;

Regenerated catalyst particles at a Aten'lperature of about 1000 F. to l150F. are withdrawn from the bottom portion of the dense uidized mass or mixture 02 in the vessel 80 by means of a well |08 arranged at one side of the regeneration vessel and formed by an upstanding partition H0 which extends for a short distance above the distribution grid member 03,r The hot, regenerated catalyst particles are introduced into the upper portion of the standpipe |05. Fluidizing gas is preferably introduced along the length of the standpipe through lines H2 to maintain the particles in the standpipe in .a luidiz'ed, liquid-simulating condition, so that a hydrostatic pressure is produced at the base of the standpipe for passing the catalyst particles into the reaction vessel l0.

The standpipe |06 is provided at its lower portion with a slide control valve i 4 for controlling the rate of withdrawal of regenerated particles from the standpipe. The slide valve ||4 isvvdesigned for a certain pressure-,drop as, for example, 5 pounds per square inch. Where the hydrov, staticA pressure developed by the standpipe |06`is greatly in excess of the design figure. and for other reasons previously described the pressuredrop or pressure differential across the slide valve H4 may be relatively large and this results in increased erosion of the slide valve. r

The construction of the constriction and the operation of my invention to reduce the pressuredrop across the slide valve H4 are substantially the same asrthose above-described in connection with the slide valve 50 and constriction 62, and

further detailed description is not believed necessary. Below slide valve Ild, a line H0 is provided having a constriction H8, which is similar to the constriction 02 above-described. Below the constriction H8 the catalyst particles flow v,into lineV I@ from which they are fed into the inlet line |2 leading int-o the reaction vessel |0.

YIn the catalytic cracking Vof hydrocarbons, the ratio of catalyst to oil by weight may be between about 5- andj35,-. With a certain selected opera tion, the .catalyst tomoil ratioA will be substantially constant-and the amount of hydrocarbon feed passed'through line |'5 willbe substantially constant. This feed is preferably split between the line I8 leading toinlet line I2 and line 20 lead` -ing to catalystline |6 above the constriction I8. When itis desired to maintain the pressure-drop or pressurediierential across the slide valve H4 substantially constant,`or when it is desiredrto compensate for iiuctuations in the pressure at the base of the standpipe |06, the amount of hydrocarbon feed passing through line above the constriction ||8 will be changed to increase or decrease the pressure-drop or pressure differential across constriction H8, to maintain Vthe pressure-drop or pressure differential across Valve I4 substantially at the desired gure, which may be about 5 pounds per square inch.

Specc examples will now be given of the ap- .plication of my invention to a commercial unit in' which about 40 tons per minutev of nely-divided catalyst of about 20C-400 mesh orflner are circulated.` The unit is designed for a pressure- -drop of about 5 pounds per square inch across the slide Valve 53 or slide valve H4. The pressure-drop. across either or both of these valves 50- and |4 may increase to about 10 pounds per square' inch, dueto the increased density of the catalyst particles or increased density of the mixture,.due to loss of nes or increase vin the depth of thebed in -the reactor or regeneration verssel or'ior numerous other reasons. To reduce Vthe pressure-drop across the valve 58 or slide .,.Valve 4, a constriction such as 62 or 8 is placed in the line 64 leading from slide valve 58 or line 6 leadingfrom slide valve I4. 'l The opening -in the constriction t2 or||8 is about 1.1 square feet.` Under these conditions, the pressure above the constriction will' be in-I creased and the pressure-drop or pressure differential across the slide Valve 58 or ||4 will be maintained at the desired gure of about 5 pounds per square inch. WhereV Athe pressure differential across the slide valve fluctuates; or where it is greatly in excess# of the desired iigure,` as, for example, where the pressure-'drop across the slide valve is about 15 pounds per square inch, I use the improved form of my invention of injecting added ga'sor vapor above the constriction and below the slide valve, and so ,proportion the flow of the gas or vapor as to increase the pressure-differential across the constriction to the desired extentfand in this manner reduce the pressuredrop across the slide valve `to the desired gure. `Where the Vslide Avalve 58 is designed for apressure-drop of about 5 pounds per square inch, and with the catalyst flowing through the opening in the slide valve at the rate of about 40 tons per Aminute,ithe unit is operating under normal conditions, i v Y When the hydrostatic pressure built up bythe vdifferential pressure across the. slide valve ||4 increases toabout 15 pounds per square inch, the valve in line 20 may be opened to permit feed to pass into line ||6 below the slide valve and above constrictiony H8. The amountof gas added is about 40 cubic feet per second to in- Y so that the pressure inthe line IB above the constriction ||8 will be correspondingly increased and the pressure-drop or pressure 'dif- `ferential across theslidevalve ||8 will be reduced to about 5 pounds v"per square inch or the desired gure.

While I have shown .one form of apparatus and different forms of operating my invention, and have included specic examples, it is to be understood that these are to be by way of illustration only, and various changes and modications may be made without departing from the spirit of my invention. Especially it is to be understood that rather than dividing the feed or air flows as previously described in order to obtain a controllable supply of gases to be injected between the slide valve andthe constriction, an entirely separate stream, such as process steam, may be used to modify the pressure drop across the constriction.

What I claim is:

1. An apparatus of the character' described in cluding a vessel, means for introducing powdered contacting material thereinto, means for introducing a gaseous fluid into the lower portion of said vessel at such a rate as to maintain a dense iluidized bed of contacting material therein, a standpipe communicating with said vessel and adapted to receive dense iiuidized contacting material from said vessel, a slide valve in the lower portion of said standpipe for controlling the rate of withdrawal of contacting material from said standpipe, a line below said valve and communicating with said standpipe, said line being provided with a constriction to introduce a pressure-drop after said valve, and means for subdividing a gaseous iiuid stream and introducing some of the gaseous fluid into said line between said constriction and said slide valve and 10 the rest of the gaseous iluid into said line after said constriction.

2. In a process wherein powdered contact material is maintained in a zone in a dense iluidized condition and is withdrawn from said zone into a standpipe to form a iluidized dense column producing hydrostatic pressure at its base and the rate of withdrawal of powdered material from the base of said column is controlled by a valve across which a decrease in pressure in the direction of solids flow occurs during withdrawal of said powdered material and the powdered material is then passed as a conned stream to a second zone, the improvement which comprises passing the powdered material through a constriction in the conined stream leaving said valve, introducing a gaseous stream between said constriction and said valve and proportioning the gaseous uid stream to control the pressure differential across said valve.

3. The process of claim 2 wherein the gaseous stream introduced between the constriction and the valve is by-passed from the feed material entering the said second zone.

HENRY J. OGORZALY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,409,751 Gerhold et al Oct.. 22, 1946 2,437,334 Roetheli Mar. 9, 1948 2,440,482 Martin Apr. 29. 1948 

2. IN A PROCESS WHEREIN POWDERED CONTACT MATERIAL IS MAINTAINED IN A ZONE IN A DENSE FLUIDIZED CONDITION AND IS WITHDRAWN FROM SAID ZONE INTO A STANDPIPE TO FORM A FLUIDIZED DENSE COLUMN PRODUCING HYDROSTATIC PRESSURE AT ITS BASE AND THE RATE OF WITHDRAWAL OF POWDERED MATERIAL FROM THE BASE OF SAID COLUMN IKS CONTROLLED BY A VALVE ACROSS WHICH A DECREASE IN PRESSURE IN THE DIRECTION OF SOLIDS FLOW OCCURS DURING WITHDRAWAL OF SAID POWDERED MATERIAL AND THE POWDERED MATERIAL IS THEN PASSED AS A CONFINED STREAM TO A SECOND ZONE, THE IMPROVEMENT WHICH COMPRISES PASSING THE POWDERED MATERIAL THROUGH A CONSTRICTION IN THE CONFINED STREAM LEAVING SAID VALVE, INTRODUCING A GASEOUS STREAM BETWEEN SAID CONSTRICTION AND SAID VALVE AND PROPORTIONING THE 